Anharmonic Coupling of Stretching Vibrations in Ice: A Periodic VSCF and VCI Description

Abstract

The anharmonicity of O-H stretching vibrations of water ice is characterized by use of a periodic implementation of the vibrational self-consistent field (VSCF) and vibrational configuration interaction (VCI) methods, which take phonon-phonon couplings explicitly into account through numerical evaluation of high-order terms of the nuclear potential. The low-temperature, proton-ordered phase of water ice (namely, ice-XI) is investigated. The net effect of a coupled anharmonic treatment of stretching modes is not just a rigid blue-shift of the respective harmonic spectral frequencies but rather a complex change of their relative spectral positions, which can not be captured by simple scaling strategies based on harmonic calculations. The adopted techniques allow for a hierarchical treatment of anharmonic terms of the nuclear potential, which is key to an effective identification of leading factors. We show that an anharmonic independent-mode approximation only describing the "intrinsic anharmonicity" of the O-H stretches is unable to capture the correct physics and that couplings among O-H stretches must be described. Inspection of harmonic normal coordinates allows to identify specific features of the O-H stretching motions which most likely enable strong mode-mode couplings. Finally, by coupling O-H stretches to all other possible modes of ice-XI (THz collective vibrations, molecular librations, bendings), we identify specific types of motion which significantly affect O-H stretching states: in particular, molecular librations are found to affect the stretching states more than molecular bendings.

CRYSTAL23: A Program for Computational Solid State Physics and Chemistry

“…The anharmonicity of O−H stretching vibrations of water ice has been characterized by use of the new periodic implementation of the VSCF and VCI methods. 269 The lowtemperature, proton-ordered phase of water ice (namely, ice-XI) has been investigated. The net effect of a coupled anharmonic treatment of stretching modes is not just a rigid blue-shift of the respective harmonic spectral frequencies but rather a complex change of their relative spectral positions, which cannot be captured by simple scaling strategies based on harmonic calculations.…”